CN101516931B - For the polymkeric substance prepared with metallocene catalyst of rotational moulding and injection-molded item - Google Patents

For the polymkeric substance prepared with metallocene catalyst of rotational moulding and injection-molded item Download PDF

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CN101516931B
CN101516931B CN200780023578.7A CN200780023578A CN101516931B CN 101516931 B CN101516931 B CN 101516931B CN 200780023578 A CN200780023578 A CN 200780023578A CN 101516931 B CN101516931 B CN 101516931B
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olefincopolymer
ethyleneα
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polymkeric substance
metallocene
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CN101516931A (en
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J·M·法利
C·R·戴维
R·克尔博
M·P·奥索维斯奇
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Univation Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/645—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/642 - C08F4/643
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Disclose by the ethyleneα-olefincopolymer making at least one supported metallocene catalyst in Gas-phase reactor, ethene contacts with alpha-olefin and formed.In some embodiments, described polymkeric substance can have: the density of 0.890 ~ 0.970g/cc; The melting index of 0.7 ~ 200dg/min; Be less than the melting index ratio of 30; Be greater than the ESCR value of 1000 hours; With 1% secant modulus being greater than 75,000psi.In further embodiment, described polymkeric substance can have: the density of 0.930g/cc ~ 0.970g/cc; The melting index of 10dg/min ~ 200dg/min; The melting index ratio of 10 ~ 25; The part weight being greater than 3g in spiral flow test and the product length being greater than 38cm; With the zero-shear viscosity being less than 150Pas.Also disclose the preparation method of these polymkeric substance.

Description

For the polymkeric substance prepared with metallocene catalyst of rotational moulding and injection-molded item
Invention field
The polyolefine that relate generally to of the present invention is prepared polyolefinic method and made thus in gas-phase fluidized-bed polymerizing reactor.
Background technology
Recently the progress obtained in polymerization and katalysis has made the many new polymerss with the physics and chemistry character of improvement of preparation of having the ability, and these polymkeric substance may be used for widely in senior goods and application.Although achieve these technical progresses in polyolefin industry, still there is general problem and new challenge.
The progress of polymerization technique has provided the high method improved with economy of more effective, throughput.Especially for illustration of these progressive be the exploitation of single-site catalyst systems.Single-site catalysts is being prepared in polyolefine very useful according to the show, and it can prepare relatively uniform multipolymer with good rate of polymerization, makes it possible to critically design the final character of the polymkeric substance of preparation.Contrast with traditional Ziegler-Natta catalyst composition, single-site catalysts composition comprises catalytic cpd, and wherein each catalyst component molecule contains one or only have a small amount of polymerization site.Metallocene is the most known single-site catalysts precursor-type, and be containing one or more π bonding part (such as, cycloalkyldiene base) and the organo-metallic coordination complex compound being selected from the atoms metal of periodic table of elements IIIB ~ VIII or group of the lanthanides that associates with it.
Industrial to development of new with the metallocene catalyst system improved, design this catalyst system and given great concern, its object is to prepare new polymers, improve operability or processibility and improve the throughput of catalyzer.The variable of metallocene catalyst comprises atoms metal, the π bonding part associated with described atoms metal or part, the type of used catalyst carrier and the reduction ratio of any catalyst activator and described catalyzer or catalyst precursor.
Unfortunately, carrying out improvement for the throughput of polymerization process, operability, processibility and economy needs to overcome some obstacles, especially when introducing new catalyzer.Discuss these a small amount of problems in patent and published patent application, these patents or application comprise: U.S. patent No.6, and 339,134, wherein discuss the method that the melting property of the polymkeric substance prepared by metallocene is improved; U.S. patent No.6,987,152, wherein discuss the impact of feed impurities on described method; U.S. patent No.6,914,027, wherein discuss fines generation, in flakes/fouling and relative heat trnasfer problem; No.2005/0137364 open with U.S. patent application, wherein discusses the problem about removing heat from polymerization reactor; Each document is incorporated to herein by reference at this.These documents particularly depict respectively face due to the unpredictability of the result relevant to new catalyst or catalyst system when introducing raw catalyst in described process with the FAQs needing to pay close attention to.
Such as, by metallocene and the polyethylene (mPE) of metallocene-type catalysis processibility usually from high-pressure polymerization process or the polyethylene adopting other catalyzer (such as Ziegler-natta catalyst) to prepare different.Such as, mPE has narrow molecular weight distributions usually, and it is tending towards more being difficult to processed.Generally speaking, molecular weight distribution is wider, and polymkeric substance is more processed.These examples illustrate and want facing challenges when making new catalyst system commercialization.
Usually, these mPE need more power of motor and produce higher forcing machine pressure to mate the rate of extrusion of LDPE.Typical mPE also has lower melt strength, and this character such as can have a negative impact to bubble stability in blown film extrusion, and they tend to occur melt fracture under business shearing rate.On the other hand, mPE and LDPE compares the physical properties demonstrating many excellences.
In addition, the reactor condition adopted in polyreaction and catalyzer also can affect many physics and chemistry character of polymkeric substance, especially molecular weight, molecular weight distribution, composition distribution, degree of crystallinity and melt temperature and extractable content content (such as, hexane extractable content) is comprised.Except the process control variable of some reactors that can regulate and control in process of production and reactant, the character of polymerisate can also change based on catalyst formulation and structure.The atoms metal of formation metallocene complex and part (π bonding part) may affect the character of the polymerisate of formation.The catalyst loading quantity of the quantity of the functional group (-OH on such as silicon-dioxide) on carrier structure, carrier, activator heap(ed) capacity and preimpregnation also may affect the product of formation.
Final user wishes to make some polymer properties improve or balance each other usually.Comprising the fusing point under given density, tear character, impact and tensile strength, heat-sealing and hot sticky character and other character.Such as, industrially wish very much to improve the heat-sealing of PE film and hot sticky character.Especially wish to reduce heat-sealing temperature, expand hot sticky window and improve Hot Tack strength, and keep low extractable content simultaneously thus meet the management expectancy for food product pack.These are improved and are usually realized by the density reducing film resin.But this may have a negative impact to other film character such as tear strength, dart impact strength, rigidity, and can reduce the melt temperature of film.In addition, in order to realize the good transparency, low haze and better processibility, usually by metallocene resin and high pressure LDPE blended, but this will improve manufacturing cost.
Other Background references comprise EP 1 300 240 A, WO 1996/00245, WO 2003/008468, WO 2003/093332, WO 2004/000919, U.S. Patent Application Publication 2005/0058847,2005/054791,2005/288443.
Therefore, there are the needs to the process modification comprising catalyst technology, described process modification is improving technique operability, polymer property and/or polymer processing.There are the needs of the metallocene catalyst to the technological flexibility of allowing raising in addition, wherein this metallocene may be used for multiple grades of being prepared on wide density and flowing scope of melt, thus makes catalyzer transition minimized and meet the product specification for specific end-use (such as rotational moulding and injection moulding) simultaneously.
Summary of the invention
In an aspect, embodiment disclosed herein relates to by the ethyleneα-olefincopolymer making at least one supported metallocene catalyst in Gas-phase reactor, ethene contacts with alpha-olefin and formed, and described multipolymer has following character: the density of 0.890-0.970g/cc; The melting index of 0.7-200dg/min; Be less than the melting index ratio (melt index ratio) of 30; Be greater than the ESCR value of 1000 hours; With 1% secant modulus being greater than 75,000psi.
In another aspect, embodiment disclosed herein relates to the method preparing ethyleneα-olefincopolymer, it comprises: by making ethene contact with metallocene catalyst with alpha-olefin under the reactor pressure of 0.7-70 bar with the temperature of reactor of 20-150 DEG C in Gas-phase reactor, to make ethene and alpha-olefine polymerizing and to form ethyleneα-olefincopolymer, wherein said ethyleneα-olefincopolymer meets following condition: the density of 0.890g/cc-0.970g/cc; The melting index of 0.7dg/min-200dg/min; Be less than the melting index ratio of 30; Be greater than the ESCR value of 1000 hours; With 1% secant modulus being greater than 75,000psi.
In another aspect, embodiment disclosed herein relates to by the ethyleneα-olefincopolymer making at least one supported metallocene catalyst in Gas-phase reactor, ethene contacts with alpha-olefin and formed, and described multipolymer has following character: the density of 0.930g/cc-0.970g/cc; The melting index of 10dg/min-200dg/min; The melting index ratio of 10-25; In spiral flow test (spiral flow test), be greater than the part weight (part weight) of 3g and be greater than the product length (part length) of 38cm; With the zero-shear viscosity being less than 150Pas.
In another aspect, embodiment disclosed herein relates to the method preparing ethyleneα-olefincopolymer, it comprises: by making ethene contact with metallocene catalyst with alpha-olefin under the reactor pressure of 0.7-70 bar with the temperature of reactor of 20-150 DEG C in Gas-phase reactor, to make ethene and alpha-olefine polymerizing and to form ethyleneα-olefincopolymer, wherein said ethyleneα-olefincopolymer meets following condition: the density of 0.930g/cc-0.970g/cc; The melting index of 10dg/min-200dg/min; The melting index ratio of 10-25; In spiral flow test, be greater than the part weight (part weight) of 3g and be greater than the product length (part length) of 38cm; With the zero-shear viscosity being less than 150Pas.
Other aspects of the present invention and advantage will be obvious from specification sheets below and appended claims.
Accompanying drawing is sketched
Crystal analysis classification (CRYSTAF) result of the embodiment of the multipolymer that metallocene of the present invention obtains compared with the multipolymer obtained with Z-N of Fig. 1 display and similar density and/or melting index.
Detailed Description Of The Invention
In an aspect, embodiment of the present invention relate to metallocene catalyst and prepare the method for polymkeric substance.Particularly, embodiment of the present invention relate to the improvement of the aspect of performance in the preparation of ethyleneα-olefincopolymer and at gained ethyleneα-olefincopolymer.
In further embodiment, the present invention relates to the metallocene catalyst for the preparation of the polymkeric substance of the stress cracking resistance with improvement and polymerization technique.In further embodiment, the present invention relates to the metallocene of the processibility with improvement.In further embodiment, the present invention relates to the metallocene of the hexane extractable content with reduction.
Metallocene catalyst compound
Metallocene catalyst compound described herein comprises " half is sandwich " and " entirely sandwich " compound, and it has and is one or morely bonded to Cp part at least one the 3rd race ~ the 12nd race's atoms metal (cyclopentadienyl and the part with the lobe such as cyclopentadienyl) and one or more leavings group be bonded at least one atoms metal described.Hereinafter these compounds are called " metallocene " or " metallocene catalyst component ".Described metallocene catalyst component can be supported on solid support material, as hereinafter further describe, and can when having or do not have to be supported when other catalyst component.In one embodiment, described one or more metallocene catalyst components of the present invention are represented by formula (I): Cp acp bmX n(I)
Wherein M is in one embodiment for being selected from the atoms metal of the 3rd race ~ the 12nd race's atom and lanthanide atom.In other embodiments, M can be selected from Ti, Zr, Hf atom.In other other embodiment, M is hafnium (Hf).Each leavings group X is chemically bound on M; Each Cp group is chemically bound on M; N is the integer of 0 or 1 ~ 4, is 1 or 2 in a specific embodiment.
Cp part is one or more ring or ring system, described ring or ring system comprise π bonding system such as cycloalkadienyl ligands and heterocyclic analogs at least partially.Cp part and the difference of the leavings group be bonded on described catalyst compound are that described part very easily can not be subject to the impact of substitution reaction or abstraction reaction.By Cp in formula (I) aand Cp bthe part represented can be identical or different cyclopentadienyl ligands or the part with the lobe such as cyclopentadienyl, its separately or the two can contain heteroatoms, and its separately or the two can be replaced by least one R group.The limiting examples of substituent R comprises and is selected from following group: hydrogen base (hydrogen radical), alkyl, thiazolinyl, alkynyl, cycloalkyl, aryl, acyl group, aroyl, alkoxyl group, aryloxy, alkylthio, dialkyl amido, alkylamidoalkyl, alkoxy carbonyl, aryloxycarbonyl, formamyl (carbomoyl), alkyl-and dialkyl-carbamoyl radicals, acyloxy, acyl amino (acylamino), aroylamino (aroylamino) and combination thereof.In one embodiment, Cp aand Cp bindependently selected from cyclopentadienyl, indenyl, tetrahydro indenyl, fluorenyl and respective substitutive derivative.(as used in this article, term " replacement " group meant after this term has upper at an arbitrary position at least one part replacing one or more hydrogen atom, described part is selected from such as following group: halogen group (such as, Cl, F, Br), hydroxyl, carbonyl, carboxyl, amido (amine group), phosphino-, alkoxyl group, phenyl, naphthyl, C 1-C 10alkyl, C 2-C 10thiazolinyl and combination thereof.The alkyl replaced and the example of aryl include but not limited to acyl group (acylradical), alkylamino, alkoxyl group, aryloxy, alkylthio, dialkyl amido, alkoxy carbonyl, aryloxycarbonyl, formamyl, alkyl-and dialkyl-carbamoyl radicals, acyloxy, acyl amino, aroylamino and combination thereof.)
In one embodiment, each leavings group X in above-mentioned formula (I) can independent selected from halo ion, hydride (hydride), C 1-12alkyl, C 2-12thiazolinyl, C 6-12aryl, C 7-20alkylaryl, C 1-12alkoxyl group, C 6-16aryloxy, C 7-18alkylaryloxy, C 1-12fluoroalkyl, C 6-12fluoro aryl and C 1-12containing the derivative of heteroatomic hydrocarbon and replacement thereof.As used in this article, word " leavings group " digital is bonded to the one or more chemical parts on the metal center of described catalyst component, it can be captured out by activator from catalyst component, thus produces olefinic polymerization or oligomeric in active material.Hereinafter will be further described described activator.
The structure of described metallocene catalyst component can take various ways perhaps, such as, at U.S. patent No.5, and 026,798, U.S. patent No.5,703,187 and U.S. patent No.5,747, in 406 describe those, comprise dimerization or oligomeric constituents, such as, at U.S. patent No.5,026,798 and U.S. patent No.6,069, disclosed in 213.Other is included in those catalyzer described in disclosed U.S. patent application No.US2005/0124487A1, US2005/0164875A1 and US2005/0148744.Each document above-mentioned is incorporated to herein by reference.In other embodiments, described metallocene can be formed by hafnium atoms metal, such as, at U.S. patent No.6, and 242, describe in 545, it is incorporated to herein by reference.
In certain embodiments, above-mentioned metallocene catalyst component can comprise its constitutional isomer or optical isomer or enantiomer (racemic mixture), and in one embodiment, it can be pure enantiomer.As used in this article, the metallocene catalyst component itself single, bridge joint, Asymmetrical substitute with racemize and/or mesoisomer does not form the metallocene catalyst component of at least two different bridge joints.
In one embodiment, described metallocene catalyst contains hafnium as atoms metal.In other embodiments, described part (π bonding part) one of at least containing cyclopentadienyl.In other embodiments, described metallocene contains chlorine leavings group.In other other embodiment, described metallocene contains fluorine leavings group.In other other embodiment, described metallocene contains methyl leavings group.
In some embodiments, described metallocene catalyst can be two (n-propyl cyclopentadienyl) hafnium X n, two (n-butyl cyclopentadienyl) hafnium X n, two (n-pentyl cyclopentadienyl) hafnium X n, (n-propyl cyclopentadienyl) (n-butyl cyclopentadienyl) hafnium X n, two [(2-trimethylsilyethyl) cyclopentadienyl] hafnium X n, two (trimethyl silyl cyclopentadienyl) hafnium X n, two (n-propyl cyclopentadienyl) the hafnium X of dimetylsilyl n, two (n-butyl cyclopentadienyl) hafnium X of dimetylsilyl n, two (1-n-propyl-2-methyl cyclopentadienyl) hafnium X n, (n-propyl cyclopentadienyl) (1-n-propyl-3-n-butyl cyclopentadienyl) hafnium X nor its combination, wherein X nas mentioned above.
In other embodiments, described metallocene catalyst can be two (n-propyl cyclopentadienyl) hafnium of two (n-propyl cyclopentadienyl) hafnium dichloride, two (n-propyl cyclopentadienyl) bifluoride hafnium or dimethyl.
For activator and the activation method of metallocene catalyst compound
Term " activator " is defined as any compound or component that can activate bulky ligand transition metallocene metal-type catalyst compound as above, such as Lewis acid or non-coordinative ionic activator or Ionizing activators or neutral metallocene catalyst component can be converted into other compound any of metallocene cation.Following situations is also within the scope of the present invention: use aikyiaiurnirsoxan beta or modified alumoxane as activator, and/or also use Ionizing activators, neutral or ion, such as three (normal-butyl) ammonium four (pentafluorophenyl group) boron or three perfluorophenyl boron metalloid precursors, it makes neutral metallocene compound ionize.The preferred active agent used together with catalyst composition of the present invention is methylaluminoxane (" MAO ").Described MAO activator can associate with carrier or be bonded on carrier, itself and described catalyst component are (such as, metallocene) association or separated from one another with described catalyst component, such as Gregory G.Hlatky at HeterogeneousSingle-Site Catalysts for Olefin Polymerization, as described in 100 (4) CHEMICALREVIEWS 1347-1374 (2000).
Many methods are had to prepare aikyiaiurnirsoxan beta and modified alumoxane, its limiting examples is described in following document: U.S. patent No.4, 665, 208, 4, 952, 540, 5, 091, 352, 5, 206, 199, 5, 204, 419, 4, 874, 734, 4, 924, 018, 4, 908, 463, 4, 968, 827, 5, 308, 815, 5, 329, 032, 5, 248, 801, 5, 235, 081, 5, 157, 137, 5, 103, 031, 5, 391, 793, 5, 391, 529, 5, 693, 838 and the open EP-A-0 561 476 in Europe, EP-B1-0279 586 and EP-A-0 594-218, WO 94/10180 open with PCT, all these documents are all incorporated to herein by reference.
But ionized compound can contain active proton, or associates with the residual ion of ionized compound certain other positively charged ion of not coordination or only loose" ligands.Described by this compound and similar compound have in following document: Europe open EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. patent No.5,153,157,5,198,401,5,066,741,5,206,197,5,241,025,5,387,568,5,384,299 and 5,502,124, all these documents are all incorporated to herein by reference.The present invention also can consider the combination of activator, the combination of such as aikyiaiurnirsoxan beta and Ionizing activators, see open WO94/07928 and WO 95/14044 of such as PCT, with U.S. patent No.5,153,157 and 5,453,410, all these documents are all incorporated to herein by reference.
Loading method
Carrier also can exist as a part for catalyst system of the present invention.For the supporting of the carrier of single-site catalysts such as metallocene and carrier, modification and activation method, such as at 1 METALLOCENE-BASED POLYOLEFINS 173-218, (J.Scheirs & W.Kaminsky writes, John Wiley & Sons, Ltd.2000) in discuss.As used in this article, term " carrier (support) " or " carrier (carrier) " commutative use and refer to any solid support material, comprise inorganic or organic support material.In one embodiment, described solid support material can be porous carrier materials.The limiting examples of solid support material comprises inorganic oxide and butter, especially following described material, such as talcum, clay, silicon-dioxide, aluminum oxide, magnesium oxide, zirconium white, ferriferous oxide, boron oxide, calcium oxide, zinc oxide, barium oxide, Thorotrast, phosphaljel, and polymkeric substance, the polystyrene of such as polyvinyl chloride and replacement, functionalized or crosslinked organic carrier, such as polystyrene divinylbenzene polyolefine or polymerizable compound, and composition thereof, and with the graphite that any one in its various forms exists.
The carrier of wishing is the inorganic oxide and the muriate that comprise the 2nd, 3,4,5,13 and 14 race's oxide compounds.In one embodiment, described solid support material comprises silicon-dioxide, aluminum oxide, silica-alumina, magnesium chloride, graphite and composition thereof.Other available carrier comprises magnesium oxide, titanium dioxide, zirconium white, polynite (as described in EP0511665B1), phyllosilicate etc.In other embodiments, the combination of solid support material can be used, include but not limited to combine such as silicon-dioxide-chromium, silica-alumina, silica-titania etc.Other solid support material can comprise those porous propylene acid based polymers described in EP0767184B1.
Catalyst system of the present invention can be prepared in a number of different manners and use.In one embodiment, described catalyzer is what do not support, preferably in liquid form, such as, at U.S. patent No.5,317,036 and 5,693,727 and Europe open EP-A-0593083 in describe, all these documents are incorporated to herein by reference.In a preferred embodiment, catalyst system of the present invention supports.The example supporting catalyst system used in the present invention is described in following patent: U.S. patent No.4, 701, 432, 4, 808, 561, 4, 912, 075, 4, 925, 821, 4, 937, 217, 5, 008, 228, 5, 238, 892, 5, 240, 894, 5, 332, 706, 5, 346, 925, 5, 422, 325, 5, 466, 649, 5, 466, 766, 5, 468, 702, 5, 529, 965, 5, 554, 704, 5, 629, 253, 5, 639, 835, 5, 625, 015, 5, 643, 847, 5, 665, 665, 5, 468, 702, 6, 090, 740 and the open WO 95/32995 of PCT, WO 95/14044, WO 96/06187 and WO 97/02297, all these documents are all incorporated to herein by reference.
In another embodiment, catalyst system of the present invention containing, for example U.S. patent No.5,473, the part that the polymkeric substance described in 202 combines, the document is all incorporated to herein by reference.In one embodiment, according to U.S. patent No.5,648, the method described in 310 is by catalyst system spraying dry of the present invention, and the document is all incorporated to herein by reference.In one embodiment, carry out functionalized according to the mode described in the open EP-A-0802203 in Europe to carrier of the present invention, or according to U.S. patent No.5,688, at least one substituting group of way selection described in 880 or leavings group, two sections of documents are all incorporated to herein by reference.
In another embodiment of the invention, supported catalyst system of the present invention comprises anti-static agents or surface-modifying agent, such as, at U.S. patent No.5, and 283,278 and the open WO 96/11960 of PCT in describe those, these documents are all incorporated to herein by reference.
Can find the preferred method preparing catalyzer of the present invention in WO 96/00245 and WO 96/00243, all these documents are all incorporated to herein by reference.
Polymerization process
Any appropriate means such as solution method, slurry process, high-pressure process and vapor phase process can be used to carry out polymerization process of the present invention.The method preparing a kind of special hope of polyolefin polymer according to the present invention is gas phase polymerization process, and it preferably adopts fluidized-bed reactor.The mode of the reactor of the type and the described reactor of operation is known and at such as U.S. patent No.3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541,270; EP-A-0 802 202 and belgian patent No.839, has complete description in 380.These patents disclose gas phase polymerization process, wherein said polymerisation medium is either mechanically agitated or fluidisation by the continuous flow of gaseous monomer and thinner.
Series connection or multistage polymerization process is comprised by other gas phase process that method of the present invention is considered.U.S. patent No.5 is also comprised by the gas phase process that the present invention considers, 627,242,5,665,818 and 5,677,375, with the method described in Europe open EP-A-0 794 200, EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421, all these documents are all incorporated to herein by reference.
Usually, polymerization process of the present invention can be continuous gas phase process, such as bed process.Fluidized-bed reactor for method of the present invention usually has reaction zone and so-called speed reduces district.Described reaction zone comprises growth polymerization composition granule, the polymer beads of formation and the bed of a small amount of granules of catalyst, and it is by the continuous flow fluidisation of gaseous monomer and thinner, thus removing is by the heat of the polyreaction of reaction zone.Optionally, some recycle gas can be cooled and compress and form liquid, it can improve the heat-removal capability of circulating current when reentering reaction zone.By simply testing and can easily determining suitable gas flow rate.The speed compensating gaseous monomer in circulating current equals the speed of taking out particulate polymer product and associated monomer from reactor, and regulates the gas composition by reactor and form with the gaseous state maintaining basic stable state in reaction zone.The gas admission velocity leaving reaction zone reduces district, makes the particle removing of carrying secretly there.More tiny can be removed in cyclonic separator and/or fine filtrator by the particle carried secretly and dust.By described gas by interchanger, remove the heat of polyreaction wherein, compress described gas within the compressor, afterwards described gas is back to reaction zone.
Method of the present invention is applicable to preparing alkene (comprising ethene) homopolymer and/or olefin copolymer, terpolymer etc., comprises the polymkeric substance comprising ethene and at least one or other alkene multiple.Described alkene can be alpha-olefin.Described alkene such as can contain 2 ~ 16 carbon atoms in one embodiment; Be ethene and the comonomer comprising 3 ~ 12 carbon atoms in another embodiment; Be ethene and the comonomer comprising 4 ~ 10 carbon atoms in another embodiment; Be ethene and the comonomer comprising 4 ~ 8 carbon atoms in another embodiment.
In embodiments, polyethylene can be prepared by method of the present invention.Described polyethylene can comprise Alathon and wherein ethylene content be the ethene at least about 50wt% of contained whole monomer and the interpretation of at least one alpha-olefin.Operable alkene comprises ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methylpent-1-alkene, 1-decene, 1-dodecylene, cetene etc. herein.Available is polyenoid such as 1 in addition, 3-hexadiene, 1,4-hexadiene, cyclopentadiene, Dicyclopentadiene (DCPD), 4-vinyl cyclohexyl-1-alkene, 1,5-cyclooctadiene, 5-vinylidene-2-norbornylene (5-vinylidene-2-norbornene) and 5-vinyl-2-norbornylene, and at the alkene that polymerisation medium situ is formed.When alkene is formed at polymerisation medium situ, the polyolefine containing long chain branching may be formed.
Other monomer that can be used in the method described by text comprises ethylenically unsaturated monomers, has the diolefine of 4 ~ 18 carbon atoms, conjugated diolefine or non-conjugated diene, polyenoid (polyene), vinyl monomer and cyclenes.The vinylbenzene that available non-limiting monomer in the present invention can comprise norbornylene, norbornadiene, iso-butylene, isoprene, vinylbenzocyclobutane, vinylbenzene, alkyl replace, ethylidene norbornene, Dicyclopentadiene (DCPD) and cyclopentenes.In another embodiment of the method described in this article, the comonomer polymerization that ethene or propylene can be different from least two kinds, optionally one of them can be diene, thus forms terpolymer.
In one embodiment, the content introducing the alpha-olefin in described multipolymer can amount to and be not more than 30mol%; Be 3 ~ 20mol% in other embodiments.Term used herein " polyethylene " is generally used for and refers to above-mentioned any or all polymkeric substance comprising ethene.
Usually hydrogen is used in olefinic polymerization to control polyolefinic final character.When using catalyst system of the present invention, the concentration (dividing potential drop) of known raising hydrogen can improve polyolefinic melt flow index (MFI) and/or the melting index (MI) of generation.Therefore MFI or MI can be subject to the impact of density of hydrogen.Amounts of hydrogen in polyreaction can be expressed as the mol ratio relative to polymerisable monomer total amount, and described polymerisable monomer is such as the mixture of ethene or ethene and hexene or propylene.The amounts of hydrogen be used in polymerization process of the present invention is realize the necessary amount of desired MFI or MI of final polyolefin resin.
In addition, often use staged reactor (staged reactor), it adopts two or more reactors of series connection, and one of them reactor preparation example such as high molecular weight component and other reactor can prepare lower-molecular-weight component.In one embodiment of the invention, polyolefine is prepared with staged gas phase reactor.Described commercial polymerization system is such as described in the following: (John Scheirs & W.Kaminsky writes 2METALLOCENE-BASED POLYOLEFINS 366-378, John Wiley & Sons, Ltd.2000); United States Patent (USP) 5,665,818, United States Patent (USP) 5,677,375 and EP-A-0 794 200.
In one embodiment, the one or more reactors in gas phase or fluidised bed polymerisation method can have the pressure of about 0.7 ~ about 70 bar (about 10 ~ about 1000psia); The pressure of about 14 ~ about 42 bar (about 200 ~ about 600psia) in another embodiment.In one embodiment, described one or more reactor can have the temperature of about 10 DEG C ~ about 150 DEG C; The temperature of about 40 DEG C in another embodiment ~ about 125 DEG C.In one embodiment, consider the sintering temperature of the polymkeric substance in reactor, can finish drilling and make described temperature of reactor by trip temperature the highest.In one embodiment, the superficial gas speed in one or more reactor can be about 0.2 ~ 1.1 meter per second (0.7 ~ 3.5 feet per second); Be about 0.3 ~ 0.8 meter per second (1.0 ~ 2.7 feet per second) in another embodiment.
In another embodiment of the invention, described polymerization process is continuous gas phase process, and it comprises step: recycle stream (comprising ethene and alpha olefin monomers) is introduced reactor by (a); B () introduces supported catalyst system; C () takes out recycle stream from reactor; D () cools described recycle stream; E () introduces extra monomer to substitute by the monomer be polymerized in reactor; F recycle stream or the described recycle stream of part are incorporated in reactor by () again; (g) from reactor, polymer product is taken out.
In embodiments of the invention, can before main polymerization, by one or more alkene under the existence of above-mentioned metallocene catalyst system, C 2-C 30alkene or alpha-olefin, comprise ethene or propylene or its combination and carry out prepolymerization.Prepolymerization can gas, solution or slurry mutually in, comprise at an elevated pressure interval or carry out continuously.Prepolymerization can adopt any olefinic monomer or combination and/or carry out under the existence of any Molecular weight controlling agents such as hydrogen.The example of pre-polymerization process see U.S. patent No.4,748,221,4,789,359,4,923,833,4,921,825,5,283,278 and 5,705,578 and the open WO97/44371 of the open EP-B-0279 863 and PCT in Europe, all these documents are all incorporated to herein by reference.
The invention is not restricted to any particular type of fluidisation or gas phase polymerization, it can carry out in single reactor or multiple reactor such as two or more tandem reactors.In embodiments, the present invention can in fluidized bed polymerization (its can be either mechanically agitated and/or gas fluidized) or carry out with those adopting gas phase, similar described above.Except known conventional gas phase polymerization method, what be also within the scope of the present invention is to use gas phase polymerization " condensation mode ", comprises " condensation mode of induction " and " liquid monomer " operation.
Embodiment of the present invention can adopt condensing mode polymerization, such as U.S. patent No.4, and 543,399; 4,588,790; 4,994,534; 5,352,749; 5,462,999 and 6,489, disclosed those in 408, each document is incorporated to herein by reference.Condensation mode method may be used for realizing higher cooling power, thus realizes higher reactor throughput.Except the condensable fluid of polymerization process itself, can also introduce polyreaction is other condensable fluid of inertia, thus induced condensing mode operation, such as by U.S. patent No.5,436, the method described in 304, described document is incorporated to herein by reference.
Other embodiment of the present invention can also use liquid monomer polymerization pattern, such as U.S. patent No.5, and 453,471; U.S. serial No.08/510,375; Disclosed those in PCT 95/09826 (US) and PCT 95/09827 (US).When operating under liquid monomer mode, only however the free liquid monomer that there is significant quantity then liquid may reside in whole polymer bed, condition is that the liquid monomer be present in bed is absorbed on the solid particulate matter that is present in bed or in solid particulate matter, the polymkeric substance that described solid particulate matter such as obtains or inert particle material (such as, carbon black, silicon-dioxide, clay, talcum and composition thereof).The monomer that operation can also make it possible to use condensing temperature more much higher than the temperature preparing conventional polyolefin in Gas-phase reactor under liquid monomer mode is to prepare polymkeric substance.
In one embodiment, available polymerization technique can be particle form polymerization or slurry process, wherein makes temperature remain on the temperature entering solution state lower than described polymkeric substance.Other slurry process comprises the method that uses circulating reactor and uses multiple series winding, parallel connection or its method of stirred reactor combined.The limiting examples of slurry process comprises continuous print circulation or stirring tank method.Equally, other example of slurry process at U.S. patent No.4,613,484 and 2METALLOCENE-BASED POLYOLEFINS 322-332 (2000) in be described.
In one embodiment, slurry phase polymerisation process uses the temperature of 1 ~ 50 bar and even larger pressure and 0 DEG C ~ 120 DEG C usually.In slurry polymerization, the suspension of solid granulates polymkeric substance is formed in liquid polymerization diluent agent medium, add wherein ethene and comonomer and normally hydrogen together with catalyzer.From reactor discontinuous or continuously removing comprise the described suspension of thinner, volatile constituent is separated and described component is circulated to reactor by (optionally after the distillation) with described polymkeric substance at this.The alkane with 3 ~ 7 carbon atoms is generally for the liquid diluent in polymerisation medium; In one embodiment, described alkane can be branched alkane.Medium used should be liquid under polymerization conditions and be relative inertness.When a propane medium is used, described method must operate under higher than the critical temperature of reaction diluent and the condition of pressure.In one embodiment, hexane or Trimethylmethane medium is used.
In an embodiment of method of the present invention, can there is metallocene type catalyst system and do not exist or be substantially devoid of any scavenging agent such as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and tri-n-hexyl aluminum and diethyl aluminum chloride, dibutyl zinc etc. condition under carry out described slurry process or vapor phase process." be substantially devoid of " and mean these compounds and to be involuntaryly added in reactor or any reactor component, and if exist, its amount is in the reactor less than 1ppm.
As noted, polymerization process of the present invention can use solution method to carry out.The limiting examples of solution method at such as U.S. patent No.4,271,060,5,001,205,5,236,998 and 5,589, be described in 555.
In another embodiment, a kind of or all described catalyzer combine with maximum metal-fatty acid compound of 15 % by weight such as aluminum stearate for the weight of catalyst system (or its component), as at such as U.S. patent No.6,300,436 and 5,283, disclosed in 278.Other suitable metal comprises the metal of other the 2nd race and 5th ~ 13 races.In another embodiment, by the solution feed of metal-fatty acid compound in reactor.In another embodiment, metal-fatty acid compound and described catalyst mix are also fed to separately in reactor.These reagent can with described catalyst mix, or reactor can be fed to when being with or without described catalyst system or its component with solution or slurry.
Polymerization process of the present invention uses the metallocene catalyst system with the improvement of optimized Metal loading amount and activator concentration.More particularly, the metallocene in the metallocene catalyst system selecting the present invention to improve in one embodiment and activator concentration all maximize to make the tap density of catalyst activity and polymer product, also make the operability of catalyzer maximize simultaneously.Polymkeric substance
Polyolefine of the present invention can with other polymkeric substance and/or additive blended and form the composition that may be used for object subsequently.Those additives comprise antioxidant, nucleator, acid scavenger, softening agent, stablizer, sanitas, whipping agent, ultraviolet absorbers, quencher, static inhibitor, surface slip agent, pigment, dyestuff and filler and solidifying agent such as superoxide.In one embodiment, these and other typical additives in polyolefin industry can be present in polyolefin compositions with the amount of 0.01 ~ 50 % by weight, be 0.1 ~ 20 % by weight in another embodiment, be 1 ~ 5 % by weight in another embodiment, the scope of wherein wishing can comprise the arbitrary combination of any weight percentage upper limit and any weight percentage lower limit.In one embodiment, antioxidant and stablizer, such as organic phosphite, hindered amine and phenol antioxidant can be present in polyolefin compositions of the present invention with the amount of 0.001 ~ 5 % by weight, being 0.01 ~ 0.8 % by weight in another embodiment, is 0.02 ~ 0.5 % by weight in another embodiment.
In one embodiment, filler can be 0.1 ~ 50 % by weight of described composition, is 0.1 ~ 25 % by weight of described composition in another embodiment, is 0.2 ~ 10 % by weight of described composition in another embodiment.The filler of wishing includes but not limited to titanium dioxide, silicon carbide, silicon-dioxide (with other oxide compound of silicon-dioxide, precipitation or non-precipitating), weisspiessglanz, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, phosphatic rock, barite powder, barium sulfate, magnesite, carbon black, rhombspar, calcium carbonate, ION Mg, Ca or Zn and Al, Cr or Fe and CO 3and/or HPO 4talcum and hydrotalcite compound (hydration or unhydrated); Silica powder, magnesiumcarbonate hydrochloride, glass fibre, clay, aluminum oxide and other metal oxide and carbonate, metal hydroxides, chromium, phosphorus and brominated flame retardant, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silicon-dioxide, organosilicon and composition thereof.These fillers can comprise known other filler any in affiliated field and protruded packing and carrier especially.
Soap also may reside in polyolefin compositions of the present invention.In one embodiment, this salt can exist with the amount of 0.001 of described composition ~ 2 % by weight, and it is 0.01 ~ 1 % by weight in another embodiment.The example of fatty acid metal salt comprises lauric acid, stearic acid, succsinic acid, stearyl lactic acid, lactic acid, phthalic acid, phenylformic acid, oxystearic acid, ricinolic acid, naphthenic acid, oleic acid, palmitinic acid and sinapinic acid, and suitable metal comprises Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb etc.The soap of wishing is selected from Magnesium Stearate, calcium stearate, sodium stearate, Zinic stearas, calcium oleate, zinc oleate and magnesium oleate.
With regard to preparing the physical method of the mixture of polyolefine and one or more additives, mixing fully should be carried out to guarantee obtained uniform mixture before being converted into end article.Being applicable to polyolefine of the present invention can be any physical form when mixing with one or more additives described.In one embodiment, mix with described additive by reactor granules (being defined as the particle of the polymkeric substance separated from polymerization reactor).The mean diameter of reactor granules is 10 microns ~ 5mm; It is 50 microns ~ 10mm in another embodiment.As selection, described polyolefine is the form of bead, and the mean diameter such as formed by melt extruding of reactor granules is the bead of 1mm ~ 6mm.
Mixing described additive with a kind of polyolefinic method is that each component is contacted in cylinder or other physical mixed device, and wherein said polyolefine is reactor granules form.If wished, melting mixing can be carried out in an extruder after this.The another kind of method mixing each component is directly at forcing machine or melting mixing is carried out to described polyolefin pellets and additive in other melting mixing device arbitrarily.
Such as any suitable mode what follows can be adopted to process polyolefine and the polyolefin compositions of gained of the present invention further: calendering, curtain coating, coating, coordinate, extrude, foam; The molding of form of ownership, comprises compression moulding, injection moulding, blowing, rotational moulding (rotomolding) and transfer mould; Film blowing or curtain coating and all films for realizing such as single shaft or diaxial orientation; Thermoforming, and lamination, pultrusion (pultrusion), stretch out (protrusion), draw and subtract (draw reduction), spunbond (spinbonding), melt-spinning, melt-blown, with fiber and the nonwoven fabric generation type of other form, and combination.The suitable processing technology of these and other form is described in such as PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp.1986).
When carrying out injection moulding to various object; because described moulding process comprises melting again and the mixing of described raw material, therefore the effect of the simple solid mixt of described bead is equivalent to crude polymer particle, granulation molten state mixture with the particle of bead or the bead of described two kinds of components.But in the compression molding process of medical device, described molten component mixes hardly, and be granulated molten mixture than described component bead and/or particle simple solid mixt more preferably.The those of skill in the art in affiliated field can determine the suitable process mixed polymkeric substance, thus balance is to the fully mixing needs of described moiety and the expectation to process economy.
Obtained polymkeric substance can contain additive, such as surface slip agent, antiblocking agent, antioxidant, pigment, filler, antifog agent, UV stablizer, static inhibitor, polymer processing aids, neutralizing agent, lubricant, tensio-active agent, pigment, dyestuff and nucleator further.Preferred additive comprises silicon-dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metallic stearate, calcium stearate, Zinic stearas, talcum, BaSO 4, diatomite, wax, carbon black, fire retardant, low-molecular-weight resin, hydrocarbon resin, granulated glass sphere etc.Described additive can exist with the known general significant quantity in affiliated field, and such as 0.001 % by weight ~ 10 % by weight.
In one embodiment, measure according to ASTM-D-1238-E (190 DEG C, 2.16kg weight), the melting index (MI) of polymkeric substance disclosed herein or (I 2) can be 0.01dg/min ~ 1000dg/min.In other embodiments, the MI of described polymkeric substance can be about 0.01dg/min ~ about 200dg/min; Be about 0.1dg/min ~ about 100dg/min in other embodiments; Be about 0.5dg/min ~ about 70dg/min in other embodiment further.
In one embodiment, the melting index ratio (I of polymkeric substance disclosed herein 5/ I 2) (I 5according to ASTM-D-1238-G, at 190 DEG C, measure under 5kg weight) can be 5 ~ 300.In other embodiments, described polymkeric substance melting index ratio can for about 10 ~ be less than 250; Be 15 ~ 200 in another embodiment; Be 20 ~ 180 in another embodiment.In other embodiments, the melting index ratio of described polymkeric substance can be 15 ~ 30; Be 15 ~ 20 in another embodiment; Be 10 ~ 40 in another embodiment; Can be 5 ~ 50 in another embodiment.
In one embodiment, melt flow ratio (melt flow ratio, the MFR) (I of polymkeric substance disclosed herein 21/ I 2, wherein I 2according to ASTM-D-1238-F, at 190 DEG C, measure under 21.6kg weight) can be 5 ~ 300; In other embodiments can for about 10 ~ be less than 250; Can be 15 ~ 200 in other embodiment further; Can be 20 ~ 180 in another embodiment.In other embodiments, the MFR of described polymkeric substance can be 15 ~ 30; Can be 10 ~ 40 in another embodiment; Can be 15 ~ 20 in another embodiment; Can be 5 ~ 50 in another embodiment.
Measure according to ASTM-D-1895 (method B), in one embodiment, the bulk density of polymkeric substance of the present invention is greater than at least 0.30g/cm 3.In another embodiment, the bulk density of polymkeric substance is 0.30 ~ 0.50g/cm 3.
Test determines density described in ASTM-D-4703-03 and ASTM-D-1505 can be used.
So can by described polyolefin film forming, molded articles, sheet material, wire and cable coating etc.Any routine techniques that affiliated field can be adopted known to form film, comprise extrude, coextrusion, lamination, blowing and curtain coating.Described film can be obtained in the following manner: adopt flat film or tubular process, afterwards by its in the plane of film along single shaft direction or along two direction orientations perpendicular to one another to identical or different degree.Orientation can reach identical degree in the two directions or can reach different degree.Especially preferredly the method for polymer film forming is included on blowing or cast film line extrude or coextrusion.
Polyolefinic working method for molded articles is discussed in such as with Publication about Document: Carraher, Jr., Charles E. (1996): POLYMER CHEMISTRY:ANINTRODUCTION, Marcel Dekker Inc., New York, 512-516, the document is incorporated to herein by reference.Polyolefin compositions of the present invention is applicable to such as film, fiber and nonwoven fabric, extrudes the object of object and moulded parts.The example of film comprises the blowing or casting films that are formed by coextrusion or laminar manner, described film can be used as shrink film, tacky film (cling film), stretched film, sealing membrane, alignment films, fast food packaging, heavily packing bag, groceries sack, baking and Frozen Food Packaging, medical package, industrial liners, barrier film etc., plastic film for agricultural use and sheet material in Food Contact and non-food contact application.Melt-blown and melt-spinning, solution spun fiber that the example of fiber comprises for preparing strainer, diaper fabrics, hygienic articles, medical clothes, geotextile etc. with weaving or nonwoven in form operate.The example extruding object comprises tube of material (tubing), medical tube of material, wire and cable coating, conduit (pipe), geomembrane and pond liner.The example of molded articles comprises single layer structure and the multilayer structure making of the form such as bottle, tank, large hollow member, rigid food containers and toy.
The polyolefinic object that other is wished of the present invention be can obtain and/or introduce by polyolefine of the present invention and trolley part, sports equipment, outdoor furniture comprised (such as, garden furniture) and playground apparatus, ship and water craft parts, and other this object.More particularly, trolley part comprises such as collision bumper, grid, decoration, mud guard and dashboard, external door and hood components, turbulence generator, windsheild, hub cap, mirror, body panel, protectiveness side filler rod and other inside and outside parts relevant with other vehicles with automobile, truck, ship.
The polyolefine that the polyolefine that can be obtained by the present invention is economically formed or obtains in conjunction with the present invention and form other useful object and article, it comprises: crate, container, wrapping material, labware, office floor pad, instrumentation sample holders and sample window; Medical use liquid storage vessel, such as, for the sack of the storage of blood or solution or IV transfusion, pouch and bottle; By wrapping material or the container of the food of radiation mode preservation, other medical device, comprise transfusion device, conduit and inhaling therapeutical instrument, and for may by γ or the medical device of ultraviolet radiation and the wrapping material of food, comprise dish, and for the wrapping material of storing liquid, especially water, dairy products or fruit juice; Container, comprises unit packaging and bulk storage containers.
The polyethylene that can be used in composition described herein can be obtained by multiple method.Described polyreaction can be carried out with solution phase methods, gas phase process etc.The Alathon and the ethyleneα-olefincopolymer that can be used for this paper can comprise linear polyethylene, described linear polyethylene comprises LLDPE (LLDPE, the density determined according to ASTM D 792 is 0.918 ~ 0.927g/cc), medium-density polyethylene (MDPE, density is 0.927 ~ 0.940g/cc), high density polyethylene(HDPE) (HDPE, density is greater than 0.940), very low density polyethylene (VLDPE, density is 0.900 ~ 0.918) and ultra-low density polyethylene (ULDPE, density is 0.860 ~ 0.899g/cc).In some embodiments, the density that can be used for Alathon herein and ethyleneα-olefincopolymer is 0.927 ~ 0.970g/cc, is 0.930 ~ 0.960g/cc in further embodiment.
The weight-average molecular weight of the polymkeric substance described in literary composition and the ratio (M of number-average molecular weight w/ M n) be usually greater than 1.5 ~ about 5, be especially greater than 2 ~ about 4.0, more preferably greater than about 2.2 ~ be less than 3.5.
Polymkeric substance of the present invention can have the composition distribution of relative narrower, as measured by composition Distribution Breadth Index (CDBI).The more details measuring the CDBI of multipolymer are well known by persons skilled in the art.See the PCT patent application WO 93/03093 such as announced on February 18th, 1993, it is all incorporated to herein by reference.CDBI is defined as the weight percentage of the copolymer molecule of co-monomer content within 50% of the total molar content intermediate value of comonomer.CDBI not containing the linear polyethylene of comonomer is defined as 100%.The data obtained by temperature rising elution classification (TREF) or crystal analysis classification (CRYSTAF) calculate CDBI, as known in the art.
Analyze in (as described below) at the CRYSTAF of the embodiment of polymkeric substance described herein, the polymkeric substance of 90% is at the peak temperature being less than crystallization in the temperature interval of 50 DEG C and have lower than 85 DEG C in CRYSTAF experiment.In further embodiment, the polymkeric substance of 90% is being less than crystallization in the temperature interval of 30 DEG C and is having the peak temperature lower than 84 DEG C in CRYSTAF experiment.In further embodiment, the polymkeric substance of 90% is being less than crystallization in the temperature interval of 20 DEG C and is having the peak temperature lower than 84 DEG C in CRYSTAF experiment.In further embodiment, the polymkeric substance of 90% is being less than crystallization in the temperature interval of 20 DEG C and is having the peak temperature lower than 82 DEG C in CRYSTAF experiment.
In one embodiment, polymkeric substance as herein described can have the CDBI being greater than 35% to 100%; There is CDBI in further embodiment that be greater than 35% to about 99%; There is the CDBI of 40% ~ 85% in further embodiment; There is the CDBI of 50% ~ 80% in further embodiment.In some embodiments, polymkeric substance as herein described can have the CDBI being greater than 60%; There is CDBI in further embodiment that be greater than 70%.In other embodiment of preferred wide CDBI wherein, described polymkeric substance can have the CDBI being less than 50%, have in further embodiment be less than 40% or be less than 30% CDBI.
In some embodiments, metallocene catalyst as herein described can allow larger technological flexibility.Have been found that metallocene as herein described can prepare the density of covering wide and the different grades of melting index scope.In certain embodiments, do not need to change catalyst precursor reduction ratio (reduction ratio) and support of the catalyst, these are often necessary when changing between the product grade prepared with other metallocenes.The technological flexibility improved can make catalyzer transition minimized, causes the substandard product of reduction potentially and eliminates the high cost operation required when conversion catalyst potentially.
In one embodiment, can will have the single metallocene catalyst of regulation carrier and precursor reduction ratio for the preparation of many grade polymer or multipolymer, it at least crosses over the density range of about 0.927g/cc ~ about 0.940g/cc; About 0.918g/cc ~ about 0.955g/cc in further embodiment; About 0.900g/cc ~ about 0.955g/cc in further embodiment; About 0.890g/cc ~ about 0.955g/cc in further embodiment.In some embodiments, described many grades can have the melting index (I of about 0.1dg/min ~ about 100dg/min 2); About 1.0dg/min ~ about 80dg/min in further embodiment; About 1.0dg/min ~ about 60dg/min in further embodiment.
In further embodiment, metallocene catalyst as herein described can cause having the product improving performance.Such as, optical property, tensile strength and the paracentesis resistance that can improve some grade when preparing under the comparatively high temps of allowing by using some metallocene catalyst is had been found that.In addition, compared with equivalent Z-N grade, the polyethylene of the multiple grade made with metallocene as herein described demonstrates advantageously high stress cracking resistance, more homogeneous axis/horizontal sample and better processibility unexpectedly.
Such as, in one embodiment, density is comprised for about 0.912g/cc ~ about 0.955g/cc, melting index (I 2) be less than 3.5 and melt flow ratio (MFR for about 0.1 ~ about 50dg/min, molecular weight distribution (Mw/Mn); I 21/ I 2) composition that is less than the ethylene ' alpha '-olefin of 25 can have the environmental stress crack resistance being greater than 1000 hours, wherein measures ESCR according to ASTM D-1693 condition B (ASTM D-1693-B).
In further embodiment, density is comprised for about 0.912g/cc ~ about 0.965g/cc, melting index (I 2) be less than 3.5 and melt flow ratio (MFR for about 0.1 ~ about 100dg/min, molecular weight distribution (Mw/Mn); I 21/ I 2) composition that is less than the ethyleneα-olefincopolymer of 25 can have and be less than the hexane extractable content of 2% (see 21C.F.R. § 177.1520 according to FDA method, on April 1st, 2005 revises, relevant to the FDA method of Food Contact (repeat cook and culinary art while) and the detailed description of requirement).
In a class embodiment as herein described, when testing according to the FDA method described in 21C.F.R. § 177.1520, described multipolymer has the hexane extractable content of 2.5% or less.
In another kind of embodiment as herein described, when testing according to the FDA method described in 21C.F.R. § 177.1520, described multipolymer has the hexane extractable content of 2.0% or less.
In another kind of embodiment as herein described, when testing according to the FDA method described in 21C.F.R. § 177.1520, described multipolymer has the hexane extractable content of 1.5% or less.
In further embodiment, hexane extractable content content can be less than 1.75%; Be less than 1.5% in further embodiment; Be less than 1.4% in further embodiment.
In further embodiment, density is comprised for about 0.912g/cc ~ about 0.965g/cc, melting index (I 2) be less than 3.5 and MFR (I for about 0.1 ~ about 100dg/min, molecular weight distribution (Mw/Mn) 21/ I 2) composition that is less than the ethyleneα-olefincopolymer of 25 multipolymer can with similar density and the melting index prepared with Z-N compares the extrudability of improvement.Such as, as compared spiral flow test data under 690 bar (10000psi) and show, metallocene copolymers can have the weight extruding length and at least large 5% of the multipolymer at least large 15% of similar density and the melting index prepared than Z-N.
In further embodiment, comprise by making at least one supported metallocene catalyst in Gas-phase reactor, the composition of ethyleneα-olefincopolymer that ethene contacts with alpha-olefin and formed can have following character: the density of 0.890 ~ 0.970g/cc; The melting index of 0.7 ~ 200dg/min; Be less than the melting index ratio of 30; Be greater than the ESCR value of 1000 hours; With 1% secant modulus being greater than 75,000psi.
In further embodiment, comprise by making at least one supported metallocene catalyst in Gas-phase reactor, the composition of ethyleneα-olefincopolymer that ethene contacts with alpha-olefin and formed can have following character: the density of 0.930g/cc ~ 0.970g/cc; The melting index of 10dg/min ~ 200dg/min; The melting index ratio of 10 ~ 25; In spiral flow test, be greater than the part weight (part weight) of 3g and be greater than the product length (partlength) of 38cm; With the zero-shear viscosity being less than 150Pas.In further embodiment, zero-shear viscosity can be less than 120Pas.
In further embodiment, when running Gas-phase reactor with condensation mode, the activity of some metallocene catalyst disclosed herein can be improved when using the condensing agent of higher level.
The more particular embodiment of described catalyst system and product analysis will be described by the following example.
Embodiment
Embodiment 1
In continuous polymerization reactor, with the different polyvinyl resins of two (n-propyl cyclopentadienyl) hafnium catalyst of loaded dimethyl for the preparation of three kinds of grades in rotational moulding and injection moulding application.These three kinds of grades have the target density of the target molten exponential sum 0.940 ~ 0.954g/cc of 1.5 ~ 80dg/min, and the resin of gained has performance as shown in table 1.Target prepared by table 1.
Sample Catalyst type Melting index (I 2) Density Intended application
Dg/min g/cc
1 Metallocene 1.4 0.9445 MHDPE; Rotational moulding
2 Metallocene 6.0 0.9404 MMDPE; Rotational moulding/injection moulding
3 Metallocene 80.6 0.9536 MHDPE; Injection moulding
CS1 Z-N 6.7 0.9521 HDPE; Injection moulding
CS2 Z-N 67.7 0.9530 HDPE; Injection moulding
Show with the preparation of described three kinds of grades of single catalyst and support of the catalyst, described catalyst system is applicable to the preparation (blowing of different densities and melting index grade, casting films, rotational moulding, injection moulding), wherein do not need to change reduction ratio or carrier, this is often needs comprising being prepared in interior polyethylene production of ziegler-natta catalyzed.
By the performance of polyethylene specimen prepared by often kind of metallocene, comprise actual melting index and the density of resulting polymers, compare with the polyethylene (comparative sample 1 and 2 (CS1 and CS2)) prepared by Ziegler-Natta catalyst as described below, wherein comparative sample has similar density and/or melting index.Each polymkeric substance listed in table 1 is ethylene-hexene co-polymers.
Sample 1-3 is made granular resin, with 200ppm IRGANOX tM1076 and 1000ppm Zinic stearas be dry mixed, and granulation.Subsequently the resin prepared completely is determined to all properties discussed herein.
The sign of sample 1-3 comprises the analysis that resin inherent nature, product property and resin workability compare.The resin inherent nature measured comprises: melt flowability; Density; The MWD measured by size exclusion chromatography, (SEC); The comonomer branching distribution measured by CRYSTAF; And the viscous-elastic behaviour to be measured by oscillatory rheological (oscillatory rheology).Product performance analysis based on sheet and injected sample comprises: the stress cracking resistance (ESCR) (measuring according to ASTM D-1693-B) in 100%Igepal (> 55dg/min MI sample) and 10%Igepal (< 10dg/min MI sample); Tensile property; 1% secant modulus; With Izod shock strength.Resin treatment compares and comprises: spiral flow test; And the hexane extractable content to be measured by FDA method (revise on April 1st, 177.1520,2005 see 21C.F.R. §, about for the FDA method of Food Contact (repeat cook and culinary art simultaneously) and the detailed description of requirement).
Melt flowability and processibility
(composition distribution) is distributed in the upper comonomer branching that measures of commercially available CRYSTAF instrument (model 200, PolymerChar S.A.).The starting time of 45 minutes at about 20-30mg polymer dissolution 60 minutes being then 100 DEG C in 30mL 1,2-dichlorobenzene (ODCB, Aldrich 99+% stablizes with 0.5g BHT/4L) at 160 DEG C.Then use the crystallization rate of 0.2K/min (0.2 DEG C/min) that polymers soln is cooled to 0 DEG C.Dual wavelength infrared detector is used for measure polymer concentration in crystallisation process (3.5 μm, 2853cm -1symmetrical flexible) and the Compensation Analysis time in baseline wander (3.6 μm).With certain temperature Monito ping at intervals strength of solution, obtain cumulative concentration curve.This curve represents the part by weight of crystalline polymer at each temperature relative to the derivative of temperature.
Respectively the CRYSTAF result of sample 2 and sample 3 is compared with CS1 and CS2 in FIG.CRYSTAF result shows metallocene rotational moulding and injection-molded item and the huge similar of Z-N control sample and points out.The width of Relative Peak is similar, although the peak crystallization temperature of sample 2 and 3 prepared of metallocene is a little less than the comparative sample 1 and 2 (CS1 and CS2) of ziegler-natta catalyzed.
In table 2 the inherent nature that sample 2 and 3 measures is compared with CS1 and CS2.Compared with the comparative sample prepared with Z-N, the molecular weight distribution (Mw/Mn) of sample prepared by metallocene and melt flow ratio (MFR) (I 21/ I 2) narrower.Table 2. resin inherent nature
Sample CS1 2 CS2 3
I 2(dg/min) 6.67 6.03 67.70 80.56
I 21(dg/min) 151.35 104.16 1604.60 1520.95
MFR(I 21/I 2) 22.68 17.26 23.70 18.88
I 5(dg/min) 18.91 15.68 195.75 209.83
MFR(I 21/I 5) 8.00 6.64 8.20 7.25
Density (g/cc) 0.9521 0.9404 0.9530 0.9536
Mn 16.342 32.673 8.191 14.452
Mw 76.205 70.731 41.169 37.366
Mz 251.185 131.887 148.142 69.154
Mw/Mn 4.66 2.16 5.02 2.59
CRYSTAF peak temperature 85.6 81.8 84.3 81.8
DSC peak melt temperature (DEG C) 132.2, unimodal 127.3, unimodal 130.3, unimodal 129.6, unimodal
Zero-shear viscosity η 0(Pa-s) 1166 1190 119 85
The spiral flow test data obtained under two kinds of pressure settings show the change in the weight of the spiral product made with the resin of similar melting index and length.Larger length and weight show the processibility (the melt flow ability improved under similar temperature and pressure) improved, and this material can allow that injection moulding machine realizes easier mold filling, shorter cycling time and realizes whole energy.As shown in table 3, lower molecular weight (I 2> 55dg/min) processibility be improved.The processibility of improvement is demonstrated, although this mPE has narrower MFR compared with comparative sample prepared by high fusion index resin and Z-N.The spiral flow test data of table 3. high fusion index resin
Sample CS2 3
I 2(dg/min) 67.70 80.56
MFR 23.7 18.9
Density (g/cc) 0.953 0.954
Injection pressure: 690 bar (10,000psi)
Length (cm) 33.0 39.0
Part weight (g) 2.88 3.15
Injection pressure: 1035 bar (15,000psi)
Length (cm) 43.0 49.0
Part weight (g) 3.40 3.67
The viscoelastic behavior of the sample prepared with dynamic stress rheometer test metallocene.Although sample 3 demonstrates better mobility (as the helicoidal flow data in table 3 show) compared with CS2, compared with CS2, sample 3 demonstrates closely similar behavior in oscillatory shear rheological experiment.
Based on the product property of piece performance (plaque property)
The performance of multiple injection-molded item is determined by shock resistance, rigidity and environmental stress crack resistance (ESCR).In this study, often kind of resin is made two class sample strip, be a kind ofly injection moulding and another kind compression moulding under ASTM condition.Use different samples to allow and compare the impact (such as shear flow affect MD/TD orientation, cool and solidify affect degree of crystallinity) of process variable on product property.The test-results of injected sample (IM) and ASTM compression moulded samples (ASTM) is listed in table 4.Except the ESCR sheet of thick 75 Mills, thick 125 Mills of all samples.Table 4. piece performance
MPE sample 2 demonstrates excellent stress cracking resistance, even if consider that it has the lower density of the CS2 for preparing than Z-N.This special feature is at fuel tank and require in the container of the other types of multi-chemical excellent tolerability valuable.There is more low melt flow and the sample 1 of density in the middle of CS1 and sample 2 and also demonstrate excellent stress cracking resistance.
As already mentioned before, sample 3 demonstrates processibility more better than CS2.Sample 3 also has the mechanical property similar to CS2, as shown in table 5.The piece performance of table 5. high fusion index resin by the hexane extractable content that FDA method obtains
The FDA specified requirement of food product pack, for general use, the content of hexane extractable content is lower than 5.3%, lower than 2.5% for " pressure pad (boil in bag) " application.When melting index height, the Midst density obtained by Z-N catalyzer can meet Section 1 requirement usually to low density product, and this is often realized by change density and/or change comonomer type, and its inherent nature prevents the threshold value of 2.5%.Metallocene described herein can produce the product in the melting index (melt indicia) of wide region and density, and does not limit by any FDA about hexane extractable content, comprises stricter " pressure pad " restriction.In some embodiments, metallocene as herein described can have and is less than the hexane extractable content of 2% (see 21C.F.R. § 177.1520 according to FDA method, on April 1st, 2005 revises, relevant to the FDA method of Food Contact (repeat cook and culinary art while) and the detailed description of requirement).In further embodiment, hexane extractable content can be less than 1.75%; Be less than 1.5% in further embodiment; Be less than 1.4% in further embodiment.
Generally speaking, the metallocene resin evaluated has higher peak melting point temperature and narrower MWD compared with suitable Z-N product.Difference on MWD may hinder the injection moulding of low melt index (~ 6dg/min) resin to extrude.Low melt index metallocene grade demonstrates favourable high stress cracking resistance (> 1000hr).And the low hexane extractable content of metallocene LLDPE product can open new market in food product pack, this is that current many Z-N products cannot be accomplished.
Advantageously, at least one embodiment, the invention provides the poly metallocene catalyst system that can be used for producing and there is the process based prediction model of improvement and the processibility of raising.In addition, this metallocene catalyst system can allow the separation of improvement, and produce the polymkeric substance being suitable for many application, described application has the strict FDA standard about polymkeric substance extractable content content.
Although just limited amount embodiment is described the present invention, that learns present disclosure one of ordinary skill in the art would recognize that other embodiments can designed and not depart from invention disclosed herein scope.Therefore, scope of the present invention should only be limited by appending claims.
Allly all to be incorporated to by reference herein to allow this all authorities of quoting at first document.In addition, all documents quoted herein, comprise testing regulation and be all incorporated to herein by reference to allow this all authorities of quoting, the degree quoted should make described disclosure consistent with description of the invention.

Claims (15)

1. prepare the method for ethyleneα-olefincopolymer for one kind, it comprises: by making other alpha-olefins of ethene and at least one contact with metallocene catalyst under the reactor pressure of 0.7-70 bar with the temperature of reactor of 20-150 DEG C in Gas-phase reactor, to make ethene and alpha-olefine polymerizing and to form ethyleneα-olefincopolymer, wherein said ethyleneα-olefincopolymer meets following condition:
A) density of 0.930g/cc ~ 0.970g/cc;
B) the melting index I of 10dg/min ~ 200dg/min 2;
C) the melt flow ratio I of 10 ~ 20 21/ I 2;
D) part weight of 3g or larger and the product length of 38cm or larger in spiral flow test;
E) zero-shear viscosity of 150Pas or less; With
F) molecular weight distribution of 2 to 4.0 is greater than; With
Wherein said metallocene is two (n-propyl cyclopentadienyl) hafnium X n;
Wherein X is selected from C 1-12alkyl; With
Wherein n is the integer of 0 or 1-4.
2. the process of claim 1 wherein that described ethyleneα-olefincopolymer has the melt flow ratio of 15 ~ 20.
3. the process of claim 1 wherein that described ethyleneα-olefincopolymer has the hexane extractable content of 2.0% or less.
4. the process of claim 1 wherein that described ethyleneα-olefincopolymer has the hexane extractable content of 1.5% or less.
5. the process of claim 1 wherein that described ethyleneα-olefincopolymer has the hexane extractable content of 1.4% or less.
6. the process of claim 1 wherein that described zero-shear viscosity is 120Pas or less.
7. the process of claim 1 wherein and to be analyzed by CRYSTAF, the described ethyleneα-olefincopolymer of 90% crystallization and there is 85 DEG C or lower peak temperature in CRYSTAF experiment in 50 DEG C or less temperature interval.
8. the process of claim 1 wherein and to be analyzed by CRYSTAF, the described ethyleneα-olefincopolymer of 90% crystallization and there is 84 DEG C or lower peak temperature in CRYSTAF experiment in 30 DEG C or less temperature interval.
9. the process of claim 1 wherein and to be analyzed by CRYSTAF, the described ethyleneα-olefincopolymer of 90% crystallization and there is 84 DEG C or lower peak temperature in CRYSTAF experiment in 20 DEG C or less temperature interval.
10. the process of claim 1 wherein and to be analyzed by CRYSTAF, the described ethyleneα-olefincopolymer of 90% crystallization and there is 82 DEG C or lower peak temperature in CRYSTAF experiment in 20 DEG C or less temperature interval.
The method of 11. any one of claim 1-10, wherein makes described metallocene catalyst contact with at least one solid support material.
The method of 12. any one of claim 1-10, wherein makes described metallocene catalyst and at least one activating agent.
The method of 13. claims 12, wherein said activator is aikyiaiurnirsoxan beta.
14. compositions comprising ethyleneα-olefincopolymer prepared by the method any one of claim 1-13.
15. goods formed by the composition of injection moulding claim 14.
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